Esteramides



Patented Dec. 3, 1 946 UNITED STATE,

Melvin De Groote, University City, and Bernhard Keiser, Webster Groves, Mo., assignors to Petrolite Corporation, Ltd., Wilmington, Del., a corporation of Delaware No Drawing. Original application June 23, 1943,

Divided and this application April 7, 1944,'Serial No. 530,042

Serial No. 492,180.

uct or compound, and to a novel method for manufacturing the same, our present applica' tion being a division of our pending application Serial No. 492,180, filed June 23,1943, now Patent No. 2,372,254fissued March 27, 1945; I "fO'ne. object of our invention is to provide a new-chemical product or compound that is capablefof various uses, but which is particularly adapted for use as a'demulsifier in the resolution or crude oil emulsions or the water -in-oil type,. I Another object is to provide-a "practicable method for manufacturing said chemical product or compound. I I a Briefly described, our new chemical product consists of a sub-resinous or semi-resinous prod not. obtained by reaction between a polybasic carboxy acid or its equivalent, such as the anhydride, and a hydroxylated esteramide-ofthe kind hereinafter described. Said hydroxylated esteramide is of the kind in which the" amido acyl radical is derived from a hydroxylated'monocarboxy acid having not over 5lecarbonatoms, and the acyloxy radical is characterized bybeiiig derivedfrom a monocarboxy detergentrforming acid having at least 8 and not more. than 32 carbon atoms. It .is Well 1 known that certain .monocarboXy organic acids containing eight carbon atoms or more, and not more than 32 carbon atoms, are characterized by. the fact that they combine with alkalies to produce soap or soap-like materials. These detergent-forming acids include ,fatty acids, resin acids, petroleum acids, etc. 'For'. the sake of convenience, these acids will be indicated by the formula R'COOH. Certain derivatives of detergent-forming acids react with'alkali to pro duce soap or soap-like materials, and are the obvious equivalent. of Y the unchanged or unmodified detergent-forming acids; ;for instance instead of fatty acids, one might em ploy" the 10 claims? (01. 260-404) This invention relates to a new chemical prodsee U, s. Patent No.2,242,837, dated May 20,- 1941,

to Shields.

Although any of the high molal monocarboxyacids can be converted into esteramides of the kind described, by conventional procedure, itis our preference to employ hydroxylated esteramides derived from higher fattyacids, rather than petroleum. acids, rosin acids, and' the like. We have found that by far the most effective demulsifying agents are obtained from unsaturated fatty acids having 18 carbon atoms. Such unsaturated fatty acids include the higher fatty acids, such as, oleic acid, ricinoleic acid, 'linoleic acid, linolenic acid, etc, One may. em-

ploy mixed fatty acids, as, for example, the fatty acids obtained by hydrolysis of cottonseed oil, soyabean oil, corn oil, etc. When our new product or compound is intended to be used as a demulsiher for resolving petroleum emulsions of the water-in-oil type, it is preferably obtained from unsaturated fatty acids, and morespecifically,

' unsaturated fatty acids containing a hydroxyl radical or unsaturated fatty'acidswhich have been subjected to oxidation or'oxyalkylation, such as oxyethylation. 5 p U The esteramides of the kind herein described may be obtained in any conventional manner. They are usually derived from the hydroxylated low molal acids themselves; .but if desirable, ,the functional equivalents'such as the anhydrides,

acyl chlorides, or other derivatives, maybe employed. suitable acids include hydroxyaceticacid chlorinated fatty acids. Instead ofthe resinacids, one might employ the hydrogenated resin acids. Instead of naphthenic acids, one-might employ brominated naphthenic acids, etc.

The fatty acidsnlare of the rtypebcommonlyQ referred to as highe'rfatty acidsy and of'cour'se,

this is-also trueinr egard to derivatives of the kind indicated, insofar that such derivatives are I obtained from higher f atty acids. The'petroleum acids include I not: 5 only: naturally-occurring naphthenic acids,.'b ut1 also acidsobtained by the oxidation of wax, paraiiin; etc. Such, acids may have as many-as 32 carbon atoms. 1 For. instance,-

(glycollic acid), hydr'0Xypr0pionic acid (lactic acid), and others. It 'is' not intended to include polyb'asic hydroxy} acids. Not only may alphahydroxy acids be employed, but one may also employ'the betahydroxy acids, for insta'ncqbetahydroxy butyric acid, betahydroxy propionic acid,

. etc. The objection to the use of such betah'ydroxy acids which contain, a hydrogen atomon the alpha carbon atom, is that they are rather unstable. Thus, on heating, they lose the elements of water, forming unsaturated acids. This is illustrated by the formation of acrylic acid from betahydroxy .propionic acid; For all practical purposes, the'two hydroxy acids'most' suitable are lactic acid and hydroxyacetic acid. In some 'instances;thereare available derivativesiof acids such as ethanolacetica'cid, propanolacetic acid, and ,the like. See U. S. Patent No. 2,238,928, dated April 22, 1941, to Cahn and Harris, and

Y particularly Example 51, on page 3. Note particularly Examples 64-66 on page i. If such acids be gconsidered as derivatives of hydroxyac'etic acid, and obtai ried hypothetically. by an oxy-- alkylation reaction involving alcoholic hydroxyl radical of hydroxyacetic acid, and ethylene oxide, then it is apparent that analogous compounds would be derivable by the use of glycid. In this connection note Examples 69 and 70 of the aforementioned Cahn and Harris patent. In actual manufacture, these particular types of acid are obtainable by other means.

The amide of such low molal hydroxy acid may be treated with an oxyalkylating agent, such as ethylene oxide, propylene oxide, butylene oxide,

or the like, so as to produce a compound of the following type:

O alkylene. OH

alkylene. H

Actually, the alkylene radical might represent an equivalent divalent radical, in which the carbon atom chain is interrupted at least once by oxygen, as

Having obtained a bis(hydroxyalkyl amide of the kind described, such compound can then be reacted in aconventional manner with a high molal acid or its equivalent, to give an esteramide, in other words,a compound of the following type:

(I? /alkylene. O O C R R C N alkylene O H A procedure that is frequently more readily adaptable is simply the reaction between a low molal acid, such as acetic acid, and a material 3 diethanolamine and acetic acid, although other appears in U. S. Patent No. 2,238,923, dated April 22, 1941, to Cahn .hHarris:

Example 0 (1) 156 grams of methyl lactate and 157.5 grams of diethanolamine were refluxed for 3 hours at 94 degrees (1., the alkalinity calculated as diethanolamine dropping from 50.5% to 5.4%. To the reaction mass 78 grams of methyl lactate were added and refluxlng was continued for 3% hours at 95 degrees C. The alkalinity dropped to 0.9% expressed as diethanolamine. The excess methyl lactate and the methyl alcohol which formed during the reaction were removed by distillation at a pressure of 10 mm. and at a temperature up to about degrees C. The reaction product was a reddish brown, water-soluble, somewhat viscous material and comprised largely or essentially the lactic acid amide of diethanolamine.

(2) 37.3 grams of the lactic acid amide of diethanolamine, produced in part (1) hereof, and 9.8 grams of lauric acid were heated together to 60 degrees C., whereupon a homogeneous solution resulted, and the heating was then continued for 20 minutes at degrees C., for 20 minutes at degrees C., for 20 minutes at degrees C., and for 15 minutes at degrees C.

manners, including those described in the patents previously mentioned. As illustrating such hydroxylated esters, reference is made to the following formulas:

In the above formulas, RCO represents the acyl radical derived from a hydroxylated acid having 5 carbon atoms or less, such as hydroxyacetic, hydroxypropionic, hydroxybutyric, etc. OHRCO represents the acyl radical of a hydroxylated acid, such as ricinoleic acid, hy'droxystearic acid, orsimilar acids obtained by oxidation, such as blown oleic acid or'acids obtained by the hydrolysis of blown olein. Such acyl radicals all contain at least 8 and not more than 32 carbon atoms and are apt to contain 18 carbon atoms. RCO is the acyl radical derived from a non-hydroxylate'd monocarboxy detergent-forming acid, particularly an unsaturated acid, such as oleic acid, linolenic acid, etc. It is understood, of course, that a mixture of fatty acids might be employed instead'of a single fatty acid; R' is a hydrocarbon radical having 4 to 12 carbon atoms. In examining the above formulas, it is to be notedthat comparable products might be obtainable from monobutanolamine, dibutano-lamine, monopropanolamine, dipropanolamine, monoglycerylamine, diglycerylamine, or the like, instead'of being derived from mono-ethanolamine or diethanolamine. Similarly, the products shown in the last two formulas are derived from trisdiydroxymethyl)aminomethane. Similar derivatives may be derived from 2-amino-2-ethy1- 1,3-prop'anediol and 2-amino-2-rnethyl-1,3-propanediol.

The hydroxylated esteramides may, of course, be derived in any other suitable way, such as reaction with ammonia, followed by oxyethylation, or some other suitable process. Thus, the low molal acids themselves, or, if desirable, the functional equivalents, such as the anhydrides, acyl chlorides, or other derivatives, may be reacted with ammonia, or a primary amine, such asany suitable alkylamine, or an alicyclic amine,

or an aralkylamine, to give the amide or substipluralityof available alcoholic hydroxyl groups for subsequent reaction with the polybasic carboxy-acid or its equivalent. However, even ifa non-hydroxylated detergent-forming acid, such as oleic acid, is employed, there still'is available under any circumstances at least one alcoholic hydroxyl radical, to wit, the hydroxyl radical or radicals of the low molal acyl radical. 1 g In this connection it may be wellto point out the following: By considering the reaction involvinghydroxyacetic acid and butylamine, the substituted amide so obtained can be reacted with'a polybasic carboxy-acid or its equivalent without further modification. However, the most desirable type of compound is derived from such low molal amides as are characterized by aplurality of alcoholic hydroxyl radicals.- Thus, if the substituted amide obtained by reaction between butylamine and hydroxyacetic acid is treated with ethylene oxide, glycid, or the like, and then reacted with oleic acid or some equivalent non-hydroxylated high molal acid, one still has available a plurality of alcoholic hydroxyl radicals. However, on treatment of suchamide with ethylene oxide, glycid, or the like, at least under certain conditions, there is formed to a very minor degree amides of certain low molal acids of the kind previously described; 1. e., it is exemplified by ethanolacetic acid. lAS a matterof fact, however, it is our preference that even under such circumstances, i. e., even where there is a plurality of alcoholic hydroxyl radicals present, the high molal acid also contains a hydroxyl group. This, ricinoleic acid is the preferred reactant employed to supply the high molal acyloxy radical; and in such instance, the hydroxyl radical,

which is part of the ricinoleyl radical, would serve as a reactive function forcombination with phthalic anhydride or the like by esterification. In this connection, it may be pointed out that .suchcompounds herein contemplated, and parentiated from being attached in an altogether 26 i. e., the low molal amide, instead of being treated with two moles of ethylene oxide or the like, might be treated with four moles or six moles of ethylene oxide, or even more.

' by the following:

different position to a ricinoleylradical or an phile in character, as compared with the ordinary, methyl radical appearing in. acetic acid or the like. I Other. procedures suggest themselves for preparation ofcompounds having a plurality of-alco holic hydroxyl radicals. For instance, in. the case ,of compounds derived fromtbutylamine, cyclohexylamine, benzylamine, or the like, one might Esteramide, Example 1 One pound mole of hydroxyacetic acid is reacted with one pound mole of monoethanolamine; and after the amide has been formed in substantial yield, the mass is then reacted with one pound mole of ricinoleic acid so as to form the ester. The reaction is illustrated by the following equations:

1. HOCH2COOH+HOC2H4NH2+ HOCH2CONHC2H4OH 2. HOCH2CONHCZH4OH+HORCOOH+ HOCHzCONHCzHrOOCROH Esteramide, Example 2 One pound mole of diethanolamine is substituted for monoethanolamine in Example 1, preceding. Esteramz'de, Example 3 Monopropanolamine, dipropanolamine, monobutanolamine, dibutanolamine, tris(hydroxymethyl) aminomethane, bis (hydroxymethyl) aminomethane, and the like, are substituted in place of monoethanolamine and diethanolamine in Examples 1 and 2, preceding.

Esteramicle, Example 4 Oleic acid is substituted for ricinoleic acid in Examples 1-3, preceding.

Esteramzde, Example 5 Esteramides of the kind obtained in Examples 14, preceding, are treated by a conventional oxyalkylation process with 1-2 moles of ethylene oxide, propylene oxide, butylene oxide, glycid, or

' the like;

Esteramide, Example 6 Methyl lactate is employed in the manner previously indicated to produce lactic acid derivatives instead of hydroxyacetic acid derivatives.

In any event, the reaction of the hydroxylated ester amide of the kind described with a polyuse glycid or the like as an oxyalkylating agent.

Another procedure involves preparing the amide from ammonia and treating such amide with an;

oxyalkylating agent, such asethylene oxide, p-ropylene oxide, butyleneoxide, glycid, or the like, to produce acompound of the following type:

'equivalentdivalent radical in which the carbon I atoiii'chairi is interrupted at le'ast' onoe'by oxygen;-

basic carboxy acid or its functional equivalent, such as the anhydride, is a well-known reaction and is nothing more or less than an esterification reaction of the kind employed to produce phthalated castor oil, phthalated ricinoleoamide, etc. For instance,.common comparable reactions are described in U. S. Patent No. 1,976,602, to De-Groote, Keiser and Adams, dated October 9, 1934, and U. S. Patent No. 2,078,652, to De Groote and Keiser, dated April 27, 1937. a

Briefly stated, the molar combination of the reactions selected depend upon the available number of hydroxyl groups and may be illustrated by the following examples:

' amide of the kind exemplified by E steramide, Ex-

amples preceding, is reacted with one pound mole of phthalic anhydride at approximately led-165 C. until esterification is complete, as indicated by the substantial elimination of one alcoh-olic hydroxyl radical. The product so obtained has one free carboxyl radical.

Final product, Example 2 The same procedure is followed as in the preceding Final product, Example 1, except that the esteramide employed is the kind exemplified by Esteramide, Example 6, instead of E'steramide, Examples 1-5, inclusive.

Final product, Example 3 The same procedure is followed as in Final product, Examples 1 and 2, except that two, moles of phthalic anhydride are employed instead of one mole; and the final product is characterized by the presence of two free carboxyl radicals.

Final product, Example 4 hydroxyl groups.

incl product, Erample 5 In the preceding examples, where phthalic anhydride is used, maleic anhydride or oxalic acid is employed. In such instances where oxalic acid is employed, it is desirable to use a lower temperature, in view of the fact that oxalic acid, or most of its functional equivalents, decompose at a temperature as high as 105, or thereabcuts, and instead, a temperature of 105 12 C. should be employed. Such lower temperature requires longer time for esterification to take place.

In certain instances, desirable productsare obtained from mcnohydroxylated esteramides.

For instance, hydroxyacetic acid, or methyl lactate, can be reacted with ethyl ethanolamine, propyl ethanolamine, ethyl propan-olamine, propyl butano-lamine, or the like, and the esteramide so obtained then reacted with a non-hydroxylated high molal acid, such as oleic acid. Such a product containing only one hydroxyl radical, to wit, the hydroxyl radical of the low molal acyl radical, can be reacted with phthalic anhydride or the like.

E-sterification can beconducted in the usual manner, simply employing heat to drive off the water formed. 'In some instances, where an 'anhydride is employed, water'may not be formed. If desired, one may pass a dried, inert gas, such as dried nitrogen gas, through the mass to hasten esterification. Esterification is also hastened at times by the presence of a mere'trace of a suitable acid, such as benzene sulfonic acid. In other instances, the reaction is most suitably conducted in the presence of an inert high boiling solvent, such as xylene. The xylene is continuously distilled under a reflux condenser, condensed by such condenser, and returned to the reaction chamber through a trap. The xylene vapors carry off the water, which is removed after fix azelaic, sebacic, etc.

:hol.

.8 being condensed by the trap. This is a conventional-procedure, commonly employed in this type ;or similar types of reaction.

Although we prefer to use phthalic anhydride as the most desirable source of the polybasic carboxy acid, one may use other polybasic carboxy acids or their anhydridessuch as succinic, malic, fumaric, citric,.maleic, adipic, tartaric, glutaric, .diphenic, naphthalic, oxalic, ,pimelic, suberic,

Naturally, a simple derivative of a polybasic acid, such as chlorophthalic acid, can be used as advantageously as phthalic acid itself, although there isno added advantage in the use of the more costly chemical compounds.

In View of the large number of .reactants and types of materials described, it maybe well to note those which we particularly prefer. It has been pointed out that we prefer to use unsaturated fatty acids as the source of the high molal acyloxy radical, and particularly the hydroxylated fatty acids commonly available, to Wit, ricinoleic acid. We prefer to use phthalic acid, maleic acid, or their anhydrides,or oxalic acid as the source of the poly-basiccarboxy acid. We prefer to use hydroxyaceticacid or its equivalent as the source of the low molal acyl radical. We prefer to use monoethanolamine or diethanolamine as the reactant for formation of the substituted amide employed for subsequent reaction to produce the esteramide.

In view of what has been said, it is apparent that the hydroxylated esteramides of the kind described ,previouslylmay be considered, for the sake of simplicity, as being inthe classof an alcohol, i. e.,'a monohydric or polyhydric, alco- If an alcohol is indicated by theformula Y'(OH)n, where nlindicates the number 1 or more-and if a polybasic acid body beindicated by the formula X(COOH)n, where n indicates the number 2 or more, then the reaction between amonohydric alcohol and a polybasic acid will result in a compound which may be indicated by the following formula: XY'(COOH) n, where n indicates the number 1 or more, and which is in reality a contraction of a more elaborate structural formula, in which X and .Y' are joined by a carboxyl radical or residue. Assuming, however, as would-be true in the majority of cases, that the alcohol actually would. be a polyhydric alcohol, and that the acid body would be polybasic in nature, for instanca'if one employed a diphthalate ofa polyhydroxylated esteramide of the kind previously described, then examination reveals that the formula might result in a combination, in which there were neither residual carboxyl radicals, nor residual hydroxyl radicals, or might result in compounds in which there were residual hydroxyl radicals, and no residual carboxyl radicals, or compounds where there might be residual carboxyl radicals and no residual hydroxyl radicals; or there might be both. This is indicated by the following:

in which q indicates a small whole number (one in the case of a monomer, and probably not over 20 and usually less than 10), and m and n indicate the number 1 or more, and m" and n indicate zero or a small or moderately-sized whole number, such as 'zero, one or more, but in any event, probably a, number not in excess of 10-15.

,Naturally, each residual hydroxyl could combine witna. phthalic acid bodyor; its equivalent, or

with a similarcompound derived from a tribasic acid, such ascitric acid; and in such event, there would be a large number-of free or uncombined carboxyl radicals present, possibly 20 or more. Actually, the preferable type of reagent would be more apt .to include less than 20, and in fact, less than 10 free hydroxyl radicals. It is not necessary to remark that the residual carboxyl radicals can be permitted to remain as such, or can be neutralized in any suitable manner, such as conversioninto salts, esters, amides, amino esters, orany othersuitable form.. Usually,such-conversion into salt form would be by means of sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, ammonium hydroxide, amylamine, butanolamine, ethanolamine, diethanolamine, triethanolamine, cyclohexanolamine, benzylamine, aniline, toluidine, etc. Conversion into the ester would be by means ofa monohydric alcohol, such as methyl alcohol,

ethyl alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, decyl alcohol, ethylene glycol, diethylene glycol, glycerol, diglycerol, triethylene glycol, or the like. One could employ an amino alcohol so as to produce anester.

We have found, however, as suggested, that the most suitable products are sub-resinous, semiresinous, or balsam-like products, and are preferably derived from polyhydroxylated reactants, i. e.,.polyhydroxylated esteramides. We have found that such products are soluble to a fairly definite extent; for instance, at least 5% in some solvent such as water, alcohol, benzene, dichlorethyl ether, acetone, cresylic :acid, or the like. This is simply another way of stating that it is preferable, ifthe product be one of the sub-resins, which are commonly referred to as an A resin, or B resin, .as distinguished from a C resin, which is'a highly infusible, insoluble resin (see Ellis, Chemistry ofSynthetic Resins, 1935, page 862, et

seq)

In recapitulating ly, the sub-resinous, semi-resinous, or balsamlike product herein contemplated may b indicated by the following formula:

significance, and y represents a small whole number not greater than 5, and represents a small whole number not greater than Z repre-' sents a hydrogen ion equivalent, such as metallic atom, organic radical, etc.

It will be noted that compounds of the type just described having at least one hydrophobe nucleus aredesignated as being polar when there is present either an unesterified hydroxyl radical, or an unesterified carboxyl radical, or both. We have. found that the polar type of material is by far the most effective for demulsification, and it is our preference to use such type. Indeed, this particular type is so much more effective for demulsification than the nonpolar type, that it may be considered in essence an invention with an invention.

The chemical products or compounds above described are adapted to be used as demulsifiers and also as plasticizers or softening agents in the manufacture of resin-like materials.

Having thus described our invention, what we claim as new and desire to secure by Letters Patent is:

what has been said previous- 1'."A sub-resinousesterification product of the in which :c and y are small whole numbers not greater than 10 and m, n, and m are small whole numbers not over 10, and including zero; Z is an acidic hydrogen atom equivalent; and X is a residue derived from a polybasic carboxy acid; and Y is a residue derived from a hydroxylated esteramide containing (a) one amido-linked acyl radical derived from a hydroxylated carboxy acid having not over 5 carbon atoms; and (b) at least one acyloxy radical derived from a monocarboxy detergent-forming acid having at least 8 and not more than 32 carbon atoms, and linked by a divalent aliphatic radical to the amido nitrogen atom.

Whole numbers not over 10, and including zero; Z is an acidic hydrogen atom equivalent; and

X is a residue derived from a polybasic carboxy ,acid; and Y is a residue derived from a hydroxylated esteramide containing (a) one amidolinked acyl radical derived from a hydroxylated carboxy acid having not over 5 carbon atoms; and (b) at least one acyloxy radical derived from a monocarboxy"detergent-forming acid having at least 8 and not more than 32 carbon atoms, and linked by a divalent aliphatic radical to the amido nitrogen atom.

3. A polar sub-resinous esterification productof the following formula:

in which :1: and y are small whole numbers not greater than 10 and m, n, and m are small whole numbers not over 10, and including zero; Z is an acidic hydrogen atom equivalent; and X is a residue derived from a polybasic carboxy acid; and Y is a residue derived from a hy-' droxylated esteramide containing (a) one amidolinked acyl radical derived from a hydroxylated in which :c' and y are small whole numbers not radical derived from a hydroxylated carboxy acid having not over 5 carbon atoms and free'from an alcoholic hydroxyl radical; and (b) at least one acyloxy radical derived from a higher unsaturated fatty acid having at'least 8 and not more than 32 carbon atoms, and linked by a divalent aliphatic radical to the amido nitrogen atom.

5. A polar sub-resinous esterification product of the following formula:

in which as and 2/ are small whole numbers notgreater than 10 and m, n, and m are small whole numbers not greater than 10, and including zero; Z is an acidic hydrogen atom equivalent; and X is a residue derived from a polybasic carboxy acid; and Y is a residue derived from a hydroxylated esteramide containing (a) one amido-linked acyl radical derived from a hydroxylated carboxy acid having not over 5 carbon atoms and free from an alcoholic hydroxyl radical; and (b) at least one acyloxy radical derived from a higher unsaturated fatty acid having 18 carbon atoms, and. linked by a divalent aliphatic radical to the amido'nitrogen atom.

6." A polar sub-resinous esterification product of the following formula:

- (OH)..(Y,,IXZ') in which a" and y are small Whole numbers not greater than 10, and m, nrand m are small whole numbers not over 10, and including zero; Z is an acidic hydrogen atom equivalent; and X is a residue derived-from a polybasic carboxy acid;

in which a," and y are small whole numbers not greater than 10 and m, n, and m are small whol numbers not over 10, and including zero; Z is an acidic hydrogenatom equivalent; and X is a residue derived from a dibasic carboxy acid; and

Y is a residue derived from a hydroxylated esteramide containing (a) one amido-linked acyl radical derived from a hydroxylated carboxy acidhaving not over 5 carbon atoms and free from 12 an alcoholic hydroxyl radical; and (b) at least one ricinoleyl oXy radical, and linked by a divalent aliphatic radical to the amido nitrogen atom.

8. A polar sub-resinous esterification product of the following formula:

in which a," and y are small whole numbers not greater than 10 and m, n, and m are small whole numbers not over 10, and including zero; Z is an acidic hydrogen atom equivalent; and X is a residue derived from phthalic acid; and Y is a residue derived from a hydroxylated esteramide containing (a) one amido-linked acyl radical derived from a hydroxylated carboxy acid having not over 5 carbon atoms and free from an alcoholic hydroxyl radical; and (b) at least one ricinoleyl oxy radical; and linked by a divalent I aliphatic radical to the'amido nitrogen atom.

9.- A polar sub-resinous esterification product of the following formula:

( QA v z) in which in and y are small wholenumbers not greater than 10 and m, n, andm' are small whole numbers not over 10, and including zero; Z is an acidic hydrogen atom equivalent; and X .is a residue derived from maleicacid; and Y is, a residue derived from a hydroxylated esteramide containingla) one amido-linked acylradical derived from a hydroxylated carboxy acid having not over 5 carbon atoms and freefromvan alco-.

greater than 10 and m, n, and m are small whole numbers not over 10, and including zero; Z is an acidic hydrogen atom equivalent; and X is a residue derived from oxalic acid; and Y is-aresidue derived from a hydroxylate'desteramide containing (a) one amido-linked acyl radical de-' rived from a hydroxylated carboxy acid having not over 5 carbon atoms; and free from an alcoholic hydroxyl radical; and (b) at least one ricinoleyl oxy radical, and linked by a divalent aliphatic radicalto the amido nitrogen'atom. MELVIN DE GROOTE.

BERNHABD KEISER. 

